Finish/polish for white leather

ABSTRACT

A finish/polish for white leather is disclosed which is an aqueous emulsion consisting essentially of (1) 5 to 15 percent by weight of a silicone-acrylate graft copolymer which consists essentially of 20 to 50 percent by weight of a silicone which consists essentially of 88 to 97 mol. percent of dimethylsiloxane units and 3 to 12 mol. percent of methylvinylsiloxane units, and 50 to 80 percent by weight of an acrylate which consists essentially of 58 to 62 percent by weight of ethyl acrylate, 32 to 40 percent by weight of methylmethacrylate and 2 to 6 percent by weight of a compound selected from the group consisting of methacrylic acid, acrylic acid and acrylonitrile, (2) 0.1 to 1.5 percent by weight of a leveling agent, (3) 2 to 4.5 percent by weight of ethylene glycol or a glycol ether, (4) 10 to 20 percent by weight of titanium dioxide, (5) 0 to 10 percent by weight of a wax, and (6) the balance water. The finish/polish can also contain as an optional ingredient from 1 to 3 percent by weight of a siloxane copolymer which consists essentially of 20 to 40 mol. percent of trimethylsiloxane units and 60 to 80 mol. percent of monomethylsiloxane units. The finish/polish of this invention does not tend to rub off and is, therefore, longer lasting, is essentially self-shining needing little or no buffing and provides a smooth finish with little or no evidence of powder or streaking.

limited States Patent [72] Inventors James R. Vaughn;

Mary V. Durkin, both of Greensboro, NC [211 App]. No. 814,799 [22] FiledApr. 9, 1969 [45] Patented Nov. 30, 1971 [73] Assignee Dow CorningCorporation Midland, Mich.

[54] FINISH/POLISH FOR WHITE LEATHER 8 Claims, No Drawings [52] US. Cl260/285 R, 117/64, 260/296 T, 260/827 [51] Int. Cl ..C08c 11/70. C08f45/52 [50] Field of Search 1 17/64;

Primary ExaminerMorris Liebman Assislan! Examiner-Samuel L. Fox

Auorneys- Robert F. Fleming. .lr., Laurence R4 Hobey and Harry D.Dingman ABSTRACT: A finish/polish for white leather is disclosed whichis an aqueous emulsion consisting essentially of( l to percent by weightof a silicone-acrylate graft copolymer which consists essentially of topercent by weight of a silicone which consists essentially of 88 to 97mol. percent of dimethylsiloxane units and 3 to 12 mol. percent ofmethylvinylsiloxane units, and 50 to 80 percent by weight of an acrylatewhich consists essentially of 58 to 62 percent by weight of ethylacrylate, 32 to 40 percent by weight of methylmethacrylate and 2 to 6percent by weight ofa compound selected from the group consisting ofmethacrylic acid, acrylic acid and acrylonitrile, (2) 0.1 to 1.5 percentby weight of a leveling agent, (3) 2 to 4.5 percent by weight ofethylene glycol or a glycol ether, (4) 10 to 20 percent by weight oftitanium dioxide, (5) 0 to 10 percent by weight of a wax. and (6) thebalance water. The finish/polish can also contain as an optionalingredient from 1 to 3 percent by weight of a siloxane copolymer whichconsists essentially of 20 to 40 mol. percent of trimethylsiloxane unitsand to mol. percent of monomethylsiloxane units. The finish/polish ofthis invention does not tend to rubolf and is, therefore, longerlasting. is essentially self-shining needing little or no buffing andprovides a smooth finish with little or no evidence of powder orstreakmg.

rmIsn/rous'nroit WHITE LEATHER SPECIFICATION This invention relates toafi'nish/polishfor white leather.

The major problem with existing white shoepolishes is that they are notdurable enough. The'polish rubs off andis easily scuffed. Other problemswith the presently available white shoe polishes is that they easilycrack as a result of polish buildup or drying of the leathercaused bythe'polish itself and/or the cleanings between applications. Moreover,the present white shoe polishes are inadequate in their ability to coverscuff marks.

Other disadvantages of the presently available white shoe polishes arethat they give a poor gloss, turn yellow with buffing, are'streaked uponapplication,they don't leave an evenfinish and they are messy to apply.

lt is an object of this invention to provide a finish/polish whichovercomes the above problems which exist with the currently availablewhite shoe polishes.

It has now been discovered that the disadvantages of the existingpolishes can be overcome and the objects ofthisinvention achieved by theuse as a' finish/polish for white leather a composition which is anaqueous emulsion consistingessentially of (-l) to 15 percent by weightof a silicone acrylate copolymer which consists'essentially of 20 to 50percent by weight of a silicone which consists essentially of 88m 9 7mol percent of dimethylsiloxane units and 3 to l2molpercent ofmethylvinylsiloxane units, and 50 to 80 percent by weight of an acrylatewhich consistsessentially of 5 8 to 62percent by weight of ethylacrylate, 32 to 40'percent by'w'eight of methylmethacrylate and 2 to 6percent by weight of a material selectedfrom the group consisting ofmethaerylie acid, acrylic acid and acrylonitrile, (2)0.l to 1.5 percentby weight of a leveling agent, (3) 2 to 4.5 percent by weight ofethylene glycol or a glycol ether, (4) to 20 percent by weight oftitanium dioxide, (5)0to 10 percent by weight of a wax, and (6) thebalance water. In addition,'in some instance's'it has been found thatthe objects of this invention can more readily be achieved when there isincluded in the above finish/polish from I to 3 percent by weight of asiloxane copolymer which consists essentially of 20 t0 40 mol percent oftrimethylsiloxane units and 60 to 80 mol percent of monomethylsiloxaneunits.

As indicated above, one essential ingredient of the finish/polish ofthis invention is 5 to percent, preferably 8 to 12 percent, by weight ofa silicone-acrylate copolymer. The silicone portion of this copolymerconstitutes to 50 percent, preferably to 35 percent, by weight of asilicone which is composed of 88 to 97, preferably 92 to 97 molp'ercentof dimethylsiloxane'units and from 3 to 12, preferably 3 to 8, molpercent of methylvinylsiloxane units. Theremaining S0 to 80 percent,preferably 65 to 75 percent, by weight of the silicone-acrylatecopolymer is composed of the acrylate portion. This acrylate portion ismade up of from 58 to 62 percent by weight of ethyl acrylate, 32 to 40percent by weight of methylmethacrylate and 2 to 6 percent by weight ofa material selected from'the group consisting of methacrylic acid,acrylic acid and acrylonitrile. Preferably, this latter material ismethacrylic acid.

In order to achieve the objects and advantages of the present invention,the silicone-acrylate copolymer employed must be prepared by emulsionpolymerization. Suitable emulsion polymerization processes for preparingthese copolymers are set forth in French Patent No. 1,491,782, thedisclosure of which is incorporated herein by reference. Essentially,inthe preferred embodiment, the process of preparing the copolymerinvolves the polymerization of the siloxane portion in emulsion first,then subsequently adding thereto the appropriate acrylate monomers andcopolymerizing the silicone and acrylate portionsinemulsion.Alternatively, the silicone and acrylate monomers can be emulsifiedtogether and then the silicone monomers polymerized first and thensubsequently adding a catalyst and causing polymerization of theresulting siloxane and the acrylate monomers to form the desiredcopolymer.

The second essential ingredient in the above finish/polish formulationis 0.l to 1.5, preferably'0.5 to 1.2, percent by weight of a levelingagent. Leveling agents improve the wetting of hydrophobic surfaces,prorhbte flow, decrease beading, ridges or thin spots during applicationof the finish/polish, and/or aids in the prevention of coagulation ofsolids or gellationof the finish/polish. Such materials are well knownin'the artand hence no usefulpur'pose would be served here in repeatingalready available detailed lists of suitable materials. By way ofillustration, tributoxyethyl'phosphate is a commercially availablematerial which has been found to be particularly suitable in theinstantformulations.

The third essential ingredient in the finish/polish formulation ofthis'invention is 2 to 4.5, preferably 2.5 to 3.5 percent by weight ofethylene glycol or a glycol ether. These materials impart freeze-thawstability to'the formulation and aid in the coalescence of thefinish/polish afterit'isapplied'to the white leather. Of thesematerials, the ethylene glycol is the preferred material to be employedat this time.

Thefourth essential ingredient of the finish/polish of this inveritionis 10 to 20, preferably l0 to 15, percent by weight of titanium dioxide.This component functions as a pigment in the formulation and ispreferably added as an emulsion or dispersion as are'the leveling agentandwax.

While a wax is not an essentialco'rnponent of the formulation, it isdesirable to have a wax present since it does contribute to a betterpolish. Generally speaking, the amount of wax employed will be in therange from 0 to l0 percent by weight. When a wax is employed it isusually preferred to include at least 1 percent by weight. The usefulwaxes in the finish/polish formulations of thisinvention include, forexample, both natural and synthetic waxes, such as, high molecularweight polyoxyalkylene glycols, beeswax, carnauba wax, ozokerite,microcrystalline hydrocarbon waxes, chlorinated paraffin waxes,petroleum waxes, aliphatic hydrocarbon waxes prepared by theFisc'her-Tropsch process, hydrogenated castor oil, myristic acid, palmwax, polyolefin waxes, polyacrylate waxes, acrylates, styrenecopolymeric waxes'and the like. Of these materials the carnauba wax isthe preferredmaterial at this present time.

The balance of the formulation is water which makes up'the vehicle forthe overall composition and is essential, of course, to the formation ofthe aqueous emulsion. While ordinary tap water can be used, if anyreasonable degree of stability is desired in the emulsion formulation itis necessary that either deionized or distilled water be employed.

Another optional ingredient that can be included advantageously in thefinish/polish compositions of this invention is a siloxane copolymerwhich consists essentially of 20 to 40 mol percent of trimethylsiloxaneunits and 60 to mol percent of monoi'nethylsiloxane units. Thiscopolymer must be prepared by emulsion polymerization'processes such asthose described in US. Pat. Nos. 2,891,920; 3,294,725; and 3,360,491.The amount of this copolymer employed should be in the range of l to 3percent by weight. The addition of this copolymer not only appears toplasticize the polymer film, and in some instances increase its tack butis most advantageously employed for the increase of gloss and smoothnesswhich it im'partstothe final finish.

The finish/polish formulations of this invention can, or course, containother optional ingredients which are conventional in such formulations.For example, there may be ineluded wetting, emulsifying and dispersingagents, stabilizers for the emulsion, pigments, perfumes, and, ofcourse, propellants if the formulation is to be used in the form of anaerosol spray. Of course, any such optional ingredients will necessarilybe selected so as to preserve the stability of the aqueous emulsion andso that no deleterious affect is hadupon the finish of the white leatherupon application of the formulation.

Now, in order that those skilled In the art may better understand howthe present invention can be practiced the following examples are givenby way of illustration and not by way of limitation. All percentsreferred to herein are by weight EXAMPLE 3 Four acrylic white shoefinish/polishes were tested against Johnson's White Shoe Polish undersimulated use conditions at l, 2 and 3 coat levels. All of theformulations prepared conunless Otherwlse Speclfied' 5 tained 3 g. ofethylene glycol, 6 g. of tributoxyethylphosphate (Primal Leveler MA-65),3 g. of wax (Primal Binder C-6). 27 EXAMPLE 1 g. of a 50 percenttitanium dioxide dispersion (Primal White 1687 about 10 percent polymersolids and the balance This example illustrates the preparation of asuitable sil- 0 water, F l i 1 contained a Commercial acrylateicone-acrylate copolymer to be employed in the composition polymer(AC-34) as the film-forming material. Fonnulation of this invention.32.99 percent of octamethyltetracyclosilox- (2 t i d th ili lat co olymr r ar d a in ane, 2.01 percent of methylvinyltetracyclosiloxane. 1percent exa l 1. Formulation (3) contained the silicone-acrylate ofdodecylbenzene sulfonic acid, 0.5 percent of the sodium copolymerprepared in example 1 and additionally about 2 salt of dodecylbenzenesulfonic acid and 63.5 percent of water percent of the siloxanecopolymer prepared in example 2. Forwere homogenized and placed in athree-necked flask mulation (4) contained an acrylate copolymer composedof equipped with a stirrer, condenser and separatory funnel. The about60 percent ethyl acrylate, 2.9 percent methacrylic acid flask was purgedwith nitrogen and then the mixture, heated at and 37.1 percentmethylmethacrylate, Let, this polymer was about 90 C. for about a halfan hour resulting in the emulsion similar to that of formulation (2)only without the silicone. polymerization of the two cyclic siloxanes togive a copolymer Formulations (l) and (4) along with the Johnson'spolish are composed of about 95 mol percent dimethylsiloxane units andincluded for purposes of comparison. about 5 mol percentmethylvinylsiloxane units. 213.1 grams of The testing of the aboveformulations was divided into se the resulting siloxane emulsion, 224.8g. of water and 17.6 g. r e eac using a se o fin an ca eathe Wooldobbers of a 1 percent solution of ammonium persulfate solution werewere used for the finish pp The objective or Series A then placed inanother three-necked flask equipped as above. was to Obtain data ggeneral appearance and water purged with nitrogen for about a half anhour and then a mix- Sistahce Clata from the DOW Corning leather teStef-Prior to ture of 104.4 g. ofethylacrylate, 5.1 g. ofmethacrylic acid andtreatment. the leather for Series A was Conditioned 16 64.5 g. ofmethylmethacrylate was added to the flask via the hours in a constanttemperature room. All leather samples separatory funnel over a period ofabout 70 minutes maintainwere from the Same hide including the controls-Coatings were ing the reaction mixture at about 70 C. Upon completion of3Wheel 16 to 24 hours apart and allowed to y in the constant theaddition of the acrylate, the flask contents were heated at temperaturereerh- 72 hours after the final coat the Samples 90 C. for about a halfan hour and then heating stopped and were run the Dow Corning leathertester according to the pH of the mixture adjusted to about 8 withammonium Procedure The conditions were as hydroxide. The resultingproduct was an aqueous emulsion of lows: a silicone-acrylate copolymerwhich consists of about 30 per- Senes PrefleXed 500 flexe5- 1 coat orfimsh and wet cent of the silicone, about 70 percent of an acrylate, theacrye late portion being composed of about 60 percent ethyl acry- Serlespreflexed 500 flexes, 2 coats of firhsh and wet late, 2.9 percentmethacrylic acid and 37.1 percent methyle methqcrylam Series A-3-preflexed 500 flexes, 3 coats of finish, dry

flexed 500 flexes, then wet flexed 3500 flexes, EXAMPLE 2 Series A4 3coats of finish and wet flexed.

The series B tests were to evaluate covering power. In this This eXamPleillustrates the Preparation of a siloxane test scuffs were made with aspatula, 1, 2 and 3 deep. A balleoPetymer composed of trlmethylshoxaheunits and point pen mark was put on the leather. Each coats coveringmonomethylsiloxane units which can be used as an optional power was thenevaluated h gloss was measured on h ingredient. A mixture of 696.8 g. ofthe deionized water and 2 Gardner m 0 Glossmeten 8- or dedeeylberlzeheSulrohle acid were Phieed hl a three- The Series D tests were toevaluate the crock resistance of necked flask q pp with stirrerCondenser and separatory the finishes. In this test a piece of greenfelt was rubbed with runner A mixture of ermethyltrlmethoxyshahe and 20pressure over the leather. Evaluation was based on the amount 8- Orhexamethyldishoxahe were Placed in a separatory tunnel of pickup on thefelt. Also resistance to household chemicals and added to the flask atroom temperature over a period of was a ured. Each material was exposedto the samples 5 about 2 hours. After the addition was complete, themixture i removed ith t li a d val d, Ch i l was stirred for anadditional 16 hours and then neutralized d i hi evaluation were 50percent h l i water. 3 with ammonium hydroxide. The result is anemulsion container ent acetic acid solution, 1 percent lvory flakesolution, a ing a siloxane copolymer which consists of about 33 mol per-50--5O mustard-catsup mixture, a l:l:l mixture of coke, cofcenttrimethylsiloxane units and about 67 mol percent fee and 5 percentcitric acid, and an oil stain. Results of these monomethylsiloxaneunits. series of evaluations are set forth in the tables below.

Series A-1 Series B Gloss Percent Flexos Percent H2O ubto penesolids OneAfter Treatment Leather Sample sorption tration pick-up Initial coatflex General appearance A 36.5 fiw Fina... Egg :"':f e: 2'

D 38.8 585 1.. A 53.1 249 0.4 6 21 11 streaked-uneven. Johnson's whiteshoe polish d0 30. 9 338 0. 4 6 22 10 D0- 0 50. 1 78 0. 5 6 26 13 D0.Formulation:

A 33. 4 838 0. 76 6 22 13 Good finish. .do {B 38.2 232 1. 2 6 22 15 D0-C 38. 3 464 0. 86 6 21 14 DO. A 52. 6 66 1. 3 6 20 11 DO. doi {a 46.3299 0.9 s 22 12 Do. C 29. 0 286 1. 2 5 25 12 D0.

Series A-3 Series B Percent Flexes Percent H10 1113- to pensolids OneTwo Three Alter Treatment Leather Sample sorption ctration I; 37.1 9642.7 185 Control (none). CalL. 403 57 D 55.9 66 A 49.9 39 6.2 7 15 20 222 streaked. Johnsons white shoe .do..... B 49.4 59 4.8 6 14 19 27 3 Do.0011s c 04. 7 7e 7. 5 7 14 20 2e 3 Do. Formulation: A 36. 2 343 9. 8 715 23 29 11 Good finish. (1).. H 410.....{3 25.6 199 5.9 o 12 18 25 Do.C 38. 0 22 5. 9 6 21 29 10 Do A 33. 9 21 11. 4 o 14 23 28 12 Do 2)do..... B 19.7 79 9.9 5 11 1s 23 6 C 54.1 600 6. 3 7 12 18 22 8 Do. A17. 6 767 7. 4 6 15 21 27 10 Do. (3)... do. B 33.7 57 3,4 6 15 22 23 12Uneven due to leather surface C 74.0 215 6.3 6 9 21 24 8 Do. A 38. 8 359. 2 5 9 17 20 5. Do. (4). .do B 40.4 28 7.1 o o 12 16 7= C 41.0 6. 9 5i) 13 14 5 D0.

Series A-4 Series B Percent Flexes Gloss 1120 to Percentabsorppenetrasolids One Two Three After General Treatment Leather Sampletlon tion pick-up Initial coat coats coats flex appearance 4 iii Control(none) .v Fina C 36.7 D 38.8 A 59.2 8 28 37 7 Strcaked Johnson's whiteshoe polish ,d B 60.1 125 0 8 32 43 39 5 D0- C 55.7 236 1.5 7 30 36 8 0.Formulation: A 68.0 121 2.4 5 23 29 33 22 Good finish (1) i0 B 45.4 9331.9 0 24 32 34 20 D0- 0 41.0 886 2.4 6 21 30 31 20 DO. A 48.4 593 2.8 622 24 28 21 Do. (2) do B 46.3 304 2.0 7 20 26 33 11) D0- C 63.4 255 2.47 21 23 26 16 Do. A 61. 4 359 4. 1 7 30 24 47 18 Do. do B 63.8 216 3.4 628 33 42 16 0 34.0 402 3.4 6 27 35 38 20 Do. A 24.8 697 3.4 8 23 29 3117 D0. (4) do B 22.3 1,100 2.4 7 24 32 32 18 Do- C 31.1 621 2. 2 6 20 2627 14 D0. 1% 37.1 42.7 Control (none) (3 11' C 40.3 D 55.9 A 37.1 5.6 713 21 26 3 streaked. ohnsons white shoe polish B 2. 2 4 4, s 0 12 20 223 Do. C 57.7 27 4.8 6 10 15 23 2 D0. ation: A 54.8 1,410 9.9 s 16 21 238 Good finish d0 {B 83. 0 184 3. 3 7 14 18 22 9 0 29. 5 260 5. 1 7 11 1921 10 Do. A 34. 6 690 8. 7 6 14 23 29 13 D0. do B 27.3 617 5.4 6 12 2023 3 0 64.5 651 9.3 6 13 23 28 10 Do. A 14. 9 182 10.0 6 14 27 36 17 Do.(3) do B 16.2 1,000 8.6 o 13 23 33 1 C 13.1 1, 276 8. 9 7 15 22 35 8 Do.A 34.0 932 8.9 5 9 18 19 7 D0. do B 28.6 097 0.0 6 12 19 23 9 o C 66.6569 7.5 6 13 20 22 8 D0.

SERIES D1.ONE COAT 0F FINISH-FILM AGED TWO DAYS Crock Ethanol Aceticacid Detergent Mustard and Coke, coflee Treatment Leather resistancesolution solution solution ketchup citric acid Oil stain Control (none)Fina No effect"... No efiect. No effect No effect No direct... Noeffect. Johnsonswhlte shoe do. Peon... Reduced $1055 .do Remove pollshStained. Stained... Removed polish.

p left circ e. Formulation:

(1). ..do very good Little efiect No efiect do. No effect No eflect. dGood. d0 Removed pollsh. do. do Do. (3). do "do do 0... D0- 410.1".Excellent.. Reducedgloss .do Little eflect, do Do.

leit circle. Control (n0ne).... Cali do No efiect .do No efiect doSlight stain Do. JOhXIXSiOIXISWhHG shoe .do.. Poor Slight circle. .doRemoved polish. Removed polish. Stained. Removed polish.

po s Formulation.

(1)... ..do Very good. Reduced gloss"... .do.. No efiect Stained Noeilectv N0 eil'ect.

(1 Good No effect ....do Removed polish. ...do .do. Do. do do do. .do:...do....... Do.

Excellent. Reduced gloss do...... do do.... d0 D0- SERIES D-Z. TWO (OATSF Fl'NISH-FILM AGED FOUR DAYS Crock Ethanol Acetic acid DetergentMustard and Coke, coffee Treatment Leather resistance solution solutionsolution ketchup citric acid Oilstain Control (none) Fina Very goodSlight circlt- No effect No efiect. Slight stain N0 efiect No effect.

Johnson s white shoe do Fair slight circle do Removed polish StainedStained Removed polish.

polish. gloss loss,

Formulation;

(1)7 d0 Excellent... Slight circle. Slight circle. d0 No effect. Noeffect 2). .7 .do Very good Glossloss. .7 No eflect... do Do (3).. 77 doFain... No efiect Slightcircle .7 .do.. ....do Do.

(4) ..do. Excellent. Slight circle No efiect. do... .do Do gloss loss.Control (none) Ca1i...... .do.. No efiect. do iiiiiiii .do7.,. Slightstain. Do. Johnlsolrlis white shoe '.7do Fain. Gloss loss Removed polish.do Stained... Removed polish pc is Formulation:

(1)7 .do. Excellent.. ..,.do... "No effect... No efiect. .7 do. Noefl'ect (2) 7 7 .do.... Very good... No efiect d D0.

(4) .do..... Excellent.7... Gloss loss Do.

SERIES D3.-THREE COATS OF FINISH-FILM AGED ONE DAY Crock Ethanol Aceticacid Detergent Mustard and Coke, coffee Treatment Leather resistancesolution solution solution ketchup citric acid Oil stain Control (none)Fina.. Very good. No effect No efiect. No efiect Stained No efl'ect Noefiect. Johnson's white Shoe ..do Fair .do do Removed do. Stained....Removed polish.

polish. polish. Formulation:

(1) No effect ..do..... No eflect (2) loss loss. D0-

(4) Gloss 1oss. D0- Gontrol (none No effect... do Do. Johnsons whiteshoe Removed Stained. Removed polish p0 polish Formulation" (1)Excellent. .do ..do No effect ..do d0 No effect.

Very good..

d0..... Excellent o ..do No effect o do Do.

EXAMPLE 4 Scuff coverage was then judged after each coat of thefinish/polish. Scuff resistance was judged after the third coat bypressing heavily the blunt end of a ballpoint pen over the surface. Theamount of scuff or mar was rated.

Two finish/polish formulations were prepared which contained thefollowing ingredients. The first formulation contained 1273 g. of a 38percent by weight aqueous emulsion of an emulsion polymerizedsilicone-acrylate copolymer which Adhesion Test consists of about 30percent by weight of a silicone which consists of 95 mol percent ofdimethylsiloxane units and 5 mol This test was made y Pressing firmlyabout 3 Inches of percent of methylvinylsiloxane units and 70 percent byweight Scotch the leather Surface after the thh'd P h of an acrylatcwhich consists of 60 percent by weight of ethyl tape is gently whim/Pdand the amount of the tthigh/Polish acrylate and 37'] percent by weightf methymethacrylate removed on the tape is noted. The results are ratedfrom poor and 2.9 percent by weight of methacrylic acid, 1776 g. of 4 oexcellent. If any of the f nish/polish is removed exposing the deionizedwater, 145.2 g. of ethylene glycol, 145.2 g. of the 5 halted a surfacerated as Poor- If of t wax of example 3, |93 6 g of the leveleroflexample 3, and finish/polish is removed, this IS ratcd as excellent.Varying 1306. 5 of a percent aqueous dispersion of titanium diox amountsof removal of the finish/polish [8 rated as fair to good. ide.

The second formulation was identical to the first except that 50 itcontained only 458.6 g. of water and in addition contained The crocktest was carried out by the use of a Crockmeter. 797 g. of a 7.2 percentsolids aqueous emulsion of an emulsion Green felt squares of about 3 cm.by 4 cm. are placed on the polymerized siloxane copolymer whichconsisted of about 29 end of a lever arm which can be cranked back andforth to mol percent trimethylsiloxane units and about 71 mol percentcover a path of about 5 inches. The felt squares are passedmonomethylsiloxane units, and 520 g. of a 7.58 percent solids across theleather samples 20 times then removed and the aqueous emulsion of anemulsion polymerized siloxane amount of finish/polish rub off is ratedfrom poor to excellent. copolymer which consisted of about 33.3 molpercent trimethylsiloxane units and about 66.7 mol percent Dtrt Testmonomethylsiloxane units.

The formulations were evaluated on leather as 0 finish/polishesemploying the following tests.

Crock Resistance The leather samples were placed in 8 ounce roundbottles which contained about 45 g. of dirt. The bottles were thenrolled for IS minutes on a mechanical roller. The samples Gloss werethen removed from the bottles and shaken off. The amount of dirtremaining on the surface is noted. The samples The Gardner portableGlossmeter was used to measure were then .wiped with a damp cloth andfurther evaluated for the gloss after one coat, two coats, and threecoats. A drying appearance. time of 24 hours was allowed between eachcoat. Two

readings of the Glossmeter were taken and averaged. water SpotRes'stance Five drops of distilled water were placed on each sampleScuff Coverage And Scuff Reslstance and allowed to stand for 5 minutes.At the end of this time, the

Before the leather samples were coated with polish, a fairly water wasblotted off. If no spot was left the results were rated severe scuff wasmade on one side of each sample by passing a as excellent; a slight spotwas rated as good; a definite water metal spatula over the same areathree times. On the opposite spot but with no swelling was rated asfair; a definite water side of the leather a simulated heel mark wasproduced by spot and with definite swelling was rated as poor; and ifthere.

passinga piece of black rubber over the same area three times. 7 5 isdye or color removal the rating of very poor wasgiven Stain Test A. l ll7r ofa silicone-acrylate copolymer consisting essentially of about 30%The leather samples are placed on a flat surface and one or ufzisilicone which consists two drops of test stain applied from aneyedropper held at a height of two to three inches above the leather.The test stain pace, memylvinylsnomnc consists of a 1 percent solutionof a purple-blue dye (Calco nits and abo 7 of an ilclyifll r 2) inwater. The stain is allowed to stand on the leather for 30 mummy 60%ethyl acryliitc. about 37% seconds and then removed with a cleansingtissue, blotter or mcthylmelhmylm and about 3% sponge and the resultsimmediately evaluated. mclhucl'ylic acid.

The results of the above described tests are set forth in the g:

. g yco c ct. following table. A a

(4) l5% llldlllul'l'l dioxide.

Scufi Scufi Crock Water spot Adhesion Dirt One Two Three TreatmentLeather resistance coverage resistance resistance Stain test test testInitial coat coats coats (1)...... Fina Fair-good... Excellent. Good. 541 4 (2). ...d o........ Fair.. 5 24 48 5'3 (1). Call. do. Good 8 13 2228 (2)..... ...do..... Fair-goo ...do. Fair. 8 14 23 31 EXAMPLE 5 (5) 0%wax. and

(6) 71% water. Four finish/polish formulations were prepared which have(I) F '*'f h f n F l t. A t d 26 3 consisting essentially of about 20% te o owing composition. ormu a ton con aine perohmmnc whichconsismsscmiuny cent of an aqueous emulsion containing 38 percent of anof about as mol percent emulsion polymerized silicone-acrylate copolymerwhich condim-hymlmne 2 i mol percent methylvinylsiloxune sisted of about30 percent by weight of a silicone which conunits and Show 80% ohm mmsists of 95 mol percent of dimethylsiloxane units and 5 mol whichconsists essentially ol'about percent of methylvinylsiloxane units, and70 percent by f *L 2% I weight of an acrylate which consists of 60percent by weight of 30 "r 'g L a ethyl acrylate and 37.1 percent byweight of methylmethacry- 2 on, trihutoxycthylphusphate. late and 2.9percent by weight of methacrylic acid, 27.8 per- (3P 2% clhylcfle s i(4) i090 titanium dioxide. cent of an aqueous emulsion containing 7.2percent solids of (s) 5% cumaubu wax and an emulsion polymerizedsiloxane copolymer which consists s 77.9 Water. of about 29 mol percenttrimethylsiloxane units and about 7l E W F JP;{Z" 50% t consistingesscntlu yo a ut mol percent monomethylsiloxane units, 8.9 percentwater, 3.0 of meme which comm percent ethylene glycol, 3.0 percent ofthe wax of example 3, essentially ol'about 97 mol percent 4.0 percent ofthe leveler of example 3 and 27.0 percent of a dimflhylsiloxene uniufmdabout! 50 percent aqueous dispersion of titanium dioxide. 40 :F IZZJZ'SFormulation B was identical to Formulation A except that itdimethylvinylsiloxane units. and contained none of the siloxanecopolymer and contained 36.7 50% of an wylaw which t Wat r consistsessentially of about 62% percen I ethyl :icryliitc. about 32%Formulation C was identical to Formu ation except that it mclhylmcmcrylmand 6% only contained 18.4 percent of the silicone-acrylateacrylonitrilc. copolymer emulsion and l6.8 percent of water. i "r t ietyenegyco. Formulation D was identical to Formulation except that it 420% uranium dioxidc contained only l8.4 percent of the stlicone-acrylate5) l0% microctyslullinc hydrocarbon wait. and copolymer emulsion,contained none of the siloxane 49% copolymer and contained 44.6 percentwater. 50 i i i i consisting essentially of about 35% These fourfinish/polish formulations were evaluated on (a silicone which consist;leather and compared to Johnson's White Shoe Polish and the essentiallyabout f mol P results of these evaluations are set forth in the tablebelow. d'mchymmmnc "i 80mol percent methylvinylsiloxune The testprocedures used were the same as those described in units, and a out as;of an acrylille example 4. which consists of about ethyl Gloss ScuffCrock Adhesion Dir One Two Three Treatment Leather coverage resistanceStain test test test Initial coat coats coats .0hn5gi1 whitt shoepolisli.. Fina Good Poor. Poor... Poor 5 7 5 5 orm 8. 10111 A.. do do.Uood. Fair-poor Excellent. 5 3i 55 5 13.. do .do Excellent Fair.......do... 6 25 8 37 C do do. Good. Fair-poor. ..do 4 5 33 42 D ..do. Fair0.... ......do r... 5 16 21 22 %ohnsgii wh1te shoe polish Call GoodPoor-fair. Very poor Poor-fair. 7 5 5 5 01m a 10H:

do .do Fair-good... Fair-poor.. Excellent ..do.. 6 18 32 3 .do. .do..Excellent. Fair... .....do.. Good 7 12 21 2 do. ....do.. Good..Fair-poor.........do....... Poor 7 20 26 S42 .do.. Fair.... ..do .doPoor-lair ..do.. 7 16 20 25 EXAMPLE 6 acrylate. about 35%methylmethucryliitc and about 5% methucrylic acid. When the followingcompositions are prepared in ac (2) Ln mhumxychylphosphm cordance withthis invention good finish/polishes are ob- (3) 2.5% mm] tained.

titanium dioxide.

(] 4% ozokerite wax to 65% water, and

(7) 3% of a siloxane copolymer which consists essentially of about 20mol percent trimethylsiloxane units and about 80 mol percentmonomethylsiloxane units.

E (l) 8% of a silicone-acrylate copolymer consistin essentially of about25% ofa silicone which consists essentially ufahout 94 mol percentdimethylsiloxane units and about 6 mol percent methylvinylsiloxaneunits, and about 75% ohm acrylate which consists of about 59% ethylacrylate, about 37% methylmethucrylate and about 4% acrylic acidv (2)0.5% tributoxyethylphosphate,

t3) 3% ethylene glycol.

(4) l4 titanium dioxide.

(5) 2% carnuuhu wax,

(6) 70.5% water. and

(7) 2% of a siloxane copolymer which consists essentially of about 40mol percent trimethylsiloxune units and 60 mol percentmonomethylsiloxane units.

That which is claimed is: l. A finish/polish for white leather which isan aqueous emulsion of l. 5 to percent by weight of a silicone-acrylategraft dimethylsiloxane units, and 3 to 12 percent of methyl-.

vinylsiloxane units, and 50 to 80 percent by weight of an acrylate whichconsists essentially of 58 to 62 percent by weight of ethyl acrylate, 32to 40 percent by weight of methylmethacrylate and 2 to 6 percent byweight of a material selected from the group consisting of methacryl icacid, acrylic acid and acrylonitrile,

2. 0.! to 1.5 percent by weight of a leveling agent,

3. 2 to 4.5 percent by weight of ethylene glycol or a glycol ether,

2. 10 to percent by weight of titanium dioxide,

5. 0 to 10 percent by weight of a wax, and

6. the balance water.

2. A finish/polish as defined in claim 1 which also contains from I to 3percent by weight of a siloxane copolymer which consists essentially of20 to 40 mol percent of trimethylsiloxane units and 60 to mol percent ofmonomethylsiloxane units.

3. A finish/polish as defined in claim 1 wherein l. is 8 to 12 percentby weight of a silicone-acrylate graft copolymer wherein the acrylicmonomers are grafted onto an already formed siloxane polymer, saidcopolymer consisting essentially of 25 to 35 percent by weight of asilicone which consists of 92 to 97 mol percent of dimethylsiloxaneunits and 3 to 8 mol percent methylvinylsiloxane units, and 65 to 75percent by weight of an acrylate which consists essentially of S8 to 62percent by weight of ethyl acrylate, 32 to 40 percent by weight ofmethylmethacrylate and 2 to 6 percent by weight of a material selectedfrom the group consisting of methacrylic acid, acrylic acid andacrylonitrile,

2. 0.5 to L2 percent by weight of a leveling agent,

3. 2.5 to 3.5 percent by weight of ethylene glycol or a glycol ether,

4. 10 to l5 percent by weight of titanium dioxide,

5. 0 to 10 percent by weight of a wax, and

6. the balance water.

4. A finish/polish as defined in claim 3 wherein (2) istributoxyethylphosphate, (3) is ethylene glycol, and there is at least 1percent by weight of wax (5).

5. A finish/polish as defined in claim 4 wherein the wax (5) is camaubawax.

6. A finish/polish as defined in claim 3 which also contains from l to 3percent by weight of a siloxane copolymer which consists essentially of20 to 40 mol percent of trimethylsiloxane units and 60 to 80 mol percentof monomethylsiloxane units.

7. A finish/polish as defined in claim 4 which also contains from i to 3percent by weight of a siloxane copolymer which consists essentially of20 to 40 mol percent of trimethylsiloxane units and 60 to 80 mol percentof monomethylsiloxane units.

8. A finish/polish as defined in claim 5 which also contains from 1 to 3percent by weight of a siloxane copolymer which consists essentially of20 to 40 mol percent of trimethylsilox ane units and 60 to 80 molpercent of monomethylsiloxane units.

2. 0.1 to 1.5 percent by weight of a leveling agent,
 2. 0.5 to 1.2percent by weight of a leveling agent,
 2. A finish/polish as defined inclaim 1 which also contains from 1 to 3 percent by weight of a siloxanecopolymer which consists essentially of 20 to 40 mol percent oftrimethylsiloxane units and 60 to 80 mol percent of monomethylsiloxaneunits.
 3. A finish/polish as defined in claim 1 wherein
 3. 2.5 to 3.5percent by weight of ethylene glycol or a glycol ether,
 3. 2 to 4.5percent by weight of ethylene glycol or a glycol ether,
 4. 10 to 20percent by weight of titanium dioxide,
 4. 10 to 15 percent by weight oftitanium dioxide,
 4. A finish/polish as defined in claim 3 wherein (2)is tributoxyethylphosphate, (3) is ethylene glycol, and there is atleast 1 percent by weight of wax (5).
 5. A finish/polish as defined inclaim 4 wherein the wax (5) is carnauba wax.
 5. 0 to 10 percent byweight of a wax, and
 5. 0 to 10 percent by weight of a wax, and
 6. thebalance water.
 6. the balance water.
 6. A finish/polish as defined inclaim 3 which also contains from 1 to 3 percent by weight of a siloxanecopolymer which consists essentially of 20 to 40 mol percent oftrimethylsiloxane units and 60 to 80 mol percent of monomethylsiloxaneunits.
 7. A finish/polish as defined in claim 4 which also contains from1 to 3 percent by weight of a siloxane copolymer which consistsessentially of 20 to 40 mol percent of trimethylsiloxane units and 60 to80 mol percent of monomethylsiloxane units.
 8. A finish/polish asdefined in claim 5 which also contains from 1 to 3 percent by weight ofa siloxane copolymer which consists essentially of 20 to 40 mol percentof trimethylsiloxane units and 60 to 80 mol percent ofmonomethylsiloxane units.